CA2468639C - Coating film formation process and coated article - Google Patents
Coating film formation process and coated article Download PDFInfo
- Publication number
- CA2468639C CA2468639C CA002468639A CA2468639A CA2468639C CA 2468639 C CA2468639 C CA 2468639C CA 002468639 A CA002468639 A CA 002468639A CA 2468639 A CA2468639 A CA 2468639A CA 2468639 C CA2468639 C CA 2468639C
- Authority
- CA
- Canada
- Prior art keywords
- coating film
- paint
- coating
- base coat
- nonvolatile component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 177
- 239000011248 coating agent Substances 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 239000003973 paint Substances 0.000 claims abstract description 180
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000000518 rheometry Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229920000877 Melamine resin Polymers 0.000 claims description 20
- 239000004640 Melamine resin Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229920002635 polyurethane Polymers 0.000 claims description 15
- 239000004814 polyurethane Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000009974 thixotropic effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000049 pigment Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000002349 favourable effect Effects 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 10
- 238000007865 diluting Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000011088 calibration curve Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- -1 ethyl acetate ester Chemical class 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ONTAEZSXZGCILH-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)-methoxyamino]methanol Chemical compound CON(CO)C1=NC(N)=NC(N)=N1 ONTAEZSXZGCILH-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- YLTSRJVQAMBSMU-UHFFFAOYSA-N [butoxy-(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound CCCCON(CO)C1=NC(N)=NC(N)=N1 YLTSRJVQAMBSMU-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- MGKZYEJERCJSLZ-UHFFFAOYSA-N COCCCCON(C1=NC(=NC(=N1)N)N)CO Chemical compound COCCCCON(C1=NC(=NC(=N1)N)N)CO MGKZYEJERCJSLZ-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 206010015535 Euphoric mood Diseases 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZDIZOOZRZQMTTD-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)-(2-methylpropoxy)amino]methanol Chemical compound CC(C)CON(CO)C1=NC(N)=NC(N)=N1 ZDIZOOZRZQMTTD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012462 polypropylene substrate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/067—Metallic effect
- B05D5/068—Metallic effect achieved by multilayers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
An object of the present invention is to provide a coating film formation process which enables the formation of a coating film excellent in the metal- tone aesthetic appearance and the invisibility of aluminum flakes. As a means of achieving this object, the coating film formation process according to the present invention is a coating film formation process comprising the steps of: coating a solvent type base coat paint (B1) onto a substrate to thus form a coating film (b1) thereon; and then, after the nonvolatile component content of the coating film (b1) has reached not lower than 40 weight %, coating a shining-material-containing aqueous base coat paint (B2) onto the coating film (b1) to thus form a coating film (b2) thereon; and then, after the nonvolatile component content of the coating film (b2) has reached not lower than 70 weight %, coating a top clear paint onto the coating film (b2) to thus form a clear coating film thereon; and thereafter carrying out simultaneous baking of the formed three layers of coating films; with the process being characterized in that, as the shining-material-containing aqueous base coat paint (B2), there is used a paint which contains a rheology control agent of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components and has a paint's nonvolatile component content of 10 to 20 weight % and a Ti value of not less than 3Ø
Description
COATING FILM FORMATION PROCESS AND COATED ARTICLE
BACKGROUND OF THE INVENTION
A. TECHNICAL FIELD
The present invention relates to: a coating film formation process which is useful for enhancing the design properties of automobile parts and parts for such as electric appliances; and a coated article having the excellent design properties as obtained by this process.
B. BACKGROUND ART
As to the automobile parts and parts for such as electric appliances, a multilayered metallic coating film is formed on these parts (made of plastic materials or metal materials) for the purpose such as of providing them with a metal-tone aesthetic appearance to thus give them a high feeling. Examples of known processes for formation of the multilayered metallic coating film include a process in what is called a 3-coat-and-l-bake manner that: a solvent type base coat paint, a shining-material-containing aqueous metallic paint, and a clear paint are coated, and then the formed three layers of coating films are simultaneously processed by baking (e.g. refer to such as patent documents 1 and 2 below). This process is commonly adopted favorably in that it is enough that the heating step for curing the coating films is once carried out. However, this process has had problems such that:
because the metallic paint is coated onto the uncured coating film surface, there is a possibility that the orientation of the shining material may become disordered to thus provide insufficient results with regard to the metal-tone aesthetic appearance or the invisibility of aluminum flakes.
[Patent Document 1]
JP-A-115094/2001 (Kokai) [Patent Document 2]
JP-A-141969/1986 (Kokai) SUMMARY OF THE INVENTION
A. OBJECT OF THE INVENTION
Thus, an object of the present invention is to provide: a coating film formation process which enables the formation of a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes; and a coated article having the excellent design properties as obtained by this process.
B. DISCLOSURE OF THE INVENTION
The present inventors diligently studied to solve the above problems. As a result, the present inventors have completed the present invention by fmding out that, in the process in which the solvent type base coat paint, the shining-material-containing aqueous base coat paint, and the top clear paint are coated in the 3-coat-and-I-bake manner, the aforementioned problems can be solved all at once by making an improvement such that: each of the step of coating the shining-material-containing aqueous base coat paint and the step of coating the top clear paint is carried out after the nonvolatile component content of each underlying coating film has come in each specific range; and further, as the shining-material-containing aqueous base coat paint, there is used a paint which has a nonvolatile component content and a Ti value in their respective specific ranges.
That is to say, a coating film formation process according to the present invention is a coating film formation process comprising the steps of: coating a solvent type base coat paint (B 1) onto a substrate to thus form a coating film (b 1) thereon; and then, after the nonvolatile component content of the coating film (b l) has reached not lower than 40 weight %, coating a shining-material-containing aqueous base coat paint (B2) onto the coating film (bl) to thus form a coating film (b2) thereon; and then, after the nonvolatile component content of the coating film (b2) has reached not lower than 70 weight %, coating a top clear paint onto the coating film (b2) to thus form a clear coating film thereon; and thereafter carrying out simultaneous baking of the formed three layers of coating films;
BACKGROUND OF THE INVENTION
A. TECHNICAL FIELD
The present invention relates to: a coating film formation process which is useful for enhancing the design properties of automobile parts and parts for such as electric appliances; and a coated article having the excellent design properties as obtained by this process.
B. BACKGROUND ART
As to the automobile parts and parts for such as electric appliances, a multilayered metallic coating film is formed on these parts (made of plastic materials or metal materials) for the purpose such as of providing them with a metal-tone aesthetic appearance to thus give them a high feeling. Examples of known processes for formation of the multilayered metallic coating film include a process in what is called a 3-coat-and-l-bake manner that: a solvent type base coat paint, a shining-material-containing aqueous metallic paint, and a clear paint are coated, and then the formed three layers of coating films are simultaneously processed by baking (e.g. refer to such as patent documents 1 and 2 below). This process is commonly adopted favorably in that it is enough that the heating step for curing the coating films is once carried out. However, this process has had problems such that:
because the metallic paint is coated onto the uncured coating film surface, there is a possibility that the orientation of the shining material may become disordered to thus provide insufficient results with regard to the metal-tone aesthetic appearance or the invisibility of aluminum flakes.
[Patent Document 1]
JP-A-115094/2001 (Kokai) [Patent Document 2]
JP-A-141969/1986 (Kokai) SUMMARY OF THE INVENTION
A. OBJECT OF THE INVENTION
Thus, an object of the present invention is to provide: a coating film formation process which enables the formation of a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes; and a coated article having the excellent design properties as obtained by this process.
B. DISCLOSURE OF THE INVENTION
The present inventors diligently studied to solve the above problems. As a result, the present inventors have completed the present invention by fmding out that, in the process in which the solvent type base coat paint, the shining-material-containing aqueous base coat paint, and the top clear paint are coated in the 3-coat-and-I-bake manner, the aforementioned problems can be solved all at once by making an improvement such that: each of the step of coating the shining-material-containing aqueous base coat paint and the step of coating the top clear paint is carried out after the nonvolatile component content of each underlying coating film has come in each specific range; and further, as the shining-material-containing aqueous base coat paint, there is used a paint which has a nonvolatile component content and a Ti value in their respective specific ranges.
That is to say, a coating film formation process according to the present invention is a coating film formation process comprising the steps of: coating a solvent type base coat paint (B 1) onto a substrate to thus form a coating film (b 1) thereon; and then, after the nonvolatile component content of the coating film (b l) has reached not lower than 40 weight %, coating a shining-material-containing aqueous base coat paint (B2) onto the coating film (bl) to thus form a coating film (b2) thereon; and then, after the nonvolatile component content of the coating film (b2) has reached not lower than 70 weight %, coating a top clear paint onto the coating film (b2) to thus form a clear coating film thereon; and thereafter carrying out simultaneous baking of the formed three layers of coating films;
2 with the process being characterized in that, as the shining-material-containing aqueous base coat paint (B2), there is used a paint which contains a rheology control agent of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components and has a paint's nonvolatile component content of 10 to 20 weight %
and a thixotropic index value of not less than 3Ø
A coated article according to the present invention is a coated article having a coating film, wherein the coating film is formed by the aforementioned coating film formation process according to the present invention.
These and other objects and the advantages of the present invention will be more fully apparent from the following detailed disclosure.
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, detailed descriptions are given about the present invention.
However, the scope of the present invention is not bound to these descriptions. And other than the following illustrations can also be carried out in the form of appropriate modifications of the following illustrations within the scope not departing from the spirit of the present invention.
The coating film formation process according to the present invention is a coating film formation process in what is called a 3-coat-and-l-bake manner comprising the steps of: coating a solvent type base coat paint (B 1) onto a substrate to thus form a coating film (b 1) (as a first coating film layer) thereon; and then coating a shining-material-containing aqueous base coat paint (B2) onto the coating film (b 1) to thus form a coating film (b2) (as a second coating film layer) thereon;
and then coating a top clear paint onto the coating film (b2) to thus form a clear coating film (as a third coating film layer) thereon; and thereafter carrying out simultaneous baking of the formed three layers of coating films. Accordingly, the coating film obtained by the coating film formation process according to the present invention has a multilayered structure such that the first coating film layer and the second coating film layer (which contains the shining material) are interposed
and a thixotropic index value of not less than 3Ø
A coated article according to the present invention is a coated article having a coating film, wherein the coating film is formed by the aforementioned coating film formation process according to the present invention.
These and other objects and the advantages of the present invention will be more fully apparent from the following detailed disclosure.
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, detailed descriptions are given about the present invention.
However, the scope of the present invention is not bound to these descriptions. And other than the following illustrations can also be carried out in the form of appropriate modifications of the following illustrations within the scope not departing from the spirit of the present invention.
The coating film formation process according to the present invention is a coating film formation process in what is called a 3-coat-and-l-bake manner comprising the steps of: coating a solvent type base coat paint (B 1) onto a substrate to thus form a coating film (b 1) (as a first coating film layer) thereon; and then coating a shining-material-containing aqueous base coat paint (B2) onto the coating film (b 1) to thus form a coating film (b2) (as a second coating film layer) thereon;
and then coating a top clear paint onto the coating film (b2) to thus form a clear coating film (as a third coating film layer) thereon; and thereafter carrying out simultaneous baking of the formed three layers of coating films. Accordingly, the coating film obtained by the coating film formation process according to the present invention has a multilayered structure such that the first coating film layer and the second coating film layer (which contains the shining material) are interposed
3 between the substrate and the third coating film layer.
The solvent type base coat paint (BI) for forming the first coating film layer in the coating film formation process according to the present invention is not especially limited. Solvent type base paints which are conventionally used are usable as such. However, favorable examples thereof include at least one member selected from among 1-package polyurethane paints, 2-package polyurethane paints, and melamine resin curing paints. In addition, the solvent type base coat paint (B 1) may contain the below-mentioned shining material (which is contained in the aqueous base coat paint (B2)) in the range of 1 to 40 weight % relative to the paint's solid components. In addition, if necessary, the solvent type base coat paint (B 1) may contain such as: color pigments (e.g. organic pigments, such as azo lake pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perynone pigments, perylene pigments, phthalonic pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and metal-complex pigments; and inorganic pigments, such as yellow iron oxide, red iron oxide, carbon black, and titanium dioxide); and extenders (e.g. talc, calcium carbonate, precipitated barium sulfate, and silica); within the range not spoiling the effects of the present invention.
Although not especially limited, the film thickness of the coating film (b 1) formed from the aforementioned solvent type base coat paint (B1) is favorably set in the range of 7 to 13 m. In the case where the film thickness of the coating film (bi) is less than 7 m, there is a possibility that the hiding power may be insufficient.
On the other hand, in the case where the film thickness of the coating film (bl) is more than 13 m, there is a possibility that, when the aqueous base coat paint (B2) is coated, the orientational defect of the shining material in the coating film (b2) may tend to occur to thus result in failure to sufficiently obtain the metal-tone aesthetic appearance, and further that popping may occur.
In the coating film formation process according to the present invention, it is
The solvent type base coat paint (BI) for forming the first coating film layer in the coating film formation process according to the present invention is not especially limited. Solvent type base paints which are conventionally used are usable as such. However, favorable examples thereof include at least one member selected from among 1-package polyurethane paints, 2-package polyurethane paints, and melamine resin curing paints. In addition, the solvent type base coat paint (B 1) may contain the below-mentioned shining material (which is contained in the aqueous base coat paint (B2)) in the range of 1 to 40 weight % relative to the paint's solid components. In addition, if necessary, the solvent type base coat paint (B 1) may contain such as: color pigments (e.g. organic pigments, such as azo lake pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perynone pigments, perylene pigments, phthalonic pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and metal-complex pigments; and inorganic pigments, such as yellow iron oxide, red iron oxide, carbon black, and titanium dioxide); and extenders (e.g. talc, calcium carbonate, precipitated barium sulfate, and silica); within the range not spoiling the effects of the present invention.
Although not especially limited, the film thickness of the coating film (b 1) formed from the aforementioned solvent type base coat paint (B1) is favorably set in the range of 7 to 13 m. In the case where the film thickness of the coating film (bi) is less than 7 m, there is a possibility that the hiding power may be insufficient.
On the other hand, in the case where the film thickness of the coating film (bl) is more than 13 m, there is a possibility that, when the aqueous base coat paint (B2) is coated, the orientational defect of the shining material in the coating film (b2) may tend to occur to thus result in failure to sufficiently obtain the metal-tone aesthetic appearance, and further that popping may occur.
In the coating film formation process according to the present invention, it is
4 important that, after the nonvolatile component content of the coating film (bl) formed from the solvent type base coat paint (Bl) has reached not lower than weight % (favorably, not lower than 60 weight %), the shining-material-containing aqueous base coat paint (B2) is coated onto the coating film (b 1). Thereby, a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes can be formed. In the case where the shining-material-containing aqueous base coat paint (B2) is coated while the nonvolatile component content of the coating film (bl) is lower than 40 weight %, then the interface between the solvent type base coat paint (B1) and the shining-material-containing aqueous base coat paint (B2) is non-uniform, so that: the cratering occurs or the metal-tone aesthetic appearance or the invisibility of aluminum flakes is spoiled.
Incidentally, such as adjustment of the vaporization speed of a diluting thinner will do for the nonvolatile component content of the coating film (b 1) to come in the aforementioned range.
In the coating film formation process according to the present invention, it is important that the shining-material -containing aqueous base coat paint (B2) for forming the second coating film layer contains a rheology control agent of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of this paint (B2). Thereby, a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes can be formed. Favorable examples of the aforementioned rheology control agent include at least one member selected from among polyether urethane resins (examples of commercially available ones include "ADEKANOL (Registered Trademark) UH-752", "ADEKANOL (Registered Trademark) UH-750", "ADEKANOL (Registered Trademark) UH-462", and "ADEKANOL (Registered Trademark) UH-814N", produced by ASAHI DENKA
CO., LTD.), polyamide compounds (examples of commercially available ones include "DISPARLON (Registered Trademark) AQ-600" produced by KUSUMOTO
CHEMICALS, LTD.), and polycarboxylic acid resins (examples of commercially
Incidentally, such as adjustment of the vaporization speed of a diluting thinner will do for the nonvolatile component content of the coating film (b 1) to come in the aforementioned range.
In the coating film formation process according to the present invention, it is important that the shining-material -containing aqueous base coat paint (B2) for forming the second coating film layer contains a rheology control agent of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of this paint (B2). Thereby, a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes can be formed. Favorable examples of the aforementioned rheology control agent include at least one member selected from among polyether urethane resins (examples of commercially available ones include "ADEKANOL (Registered Trademark) UH-752", "ADEKANOL (Registered Trademark) UH-750", "ADEKANOL (Registered Trademark) UH-462", and "ADEKANOL (Registered Trademark) UH-814N", produced by ASAHI DENKA
CO., LTD.), polyamide compounds (examples of commercially available ones include "DISPARLON (Registered Trademark) AQ-600" produced by KUSUMOTO
CHEMICALS, LTD.), and polycarboxylic acid resins (examples of commercially
5 available ones include: "PRIMAL (Registered Trademark) ASE-60" produced by ROHM and HAAS JAPAN K. K.; and "VISCALEX (Registered Trademark) HV-30"
produced by CLARIANT (JAPAN) K. K.). It is the polyether urethane resins that are favorable particularly of these. In the case where the amount of the rheology control agent in the aqueous base coat paint (B2) is smaller than the aforementioned range, it follows that the Ti value is so low as to fail to sufficiently provide the metal-tone aesthetic appearance and the invisibility of aluminum flakes. On the other hand, in the case where the amount of the rheology control agent in the aqueous base coat paint (B2) is larger than the aforementioned range, it follows that problems are brought about in that the coating operation is difficult, and further in that the storage stability is deteriorated. More favorable modes are as follows:
when the rheology control agent is the polyether urethane resin, its content is in the range of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of the paint (B2); when the rheology control agent is the polyamide compound, its content is in the range of 2.0 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of the paint (B2); and when the rheology control agent is the polycarboxylic acid resin, its content is in the range of 2.0 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of the paint (B2).
It is important that the aforementioned shining-material-containing aqueous base coat paint (B2) has a paint's nonvolatile component content (during the coating) of 10 to 20 weight % (favorably, 10 to 18 weight %) and a Ti value (thixotropic index) value) (during the coating) of not less than 3Ø Thereby, a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes can be formed. In the case where the paint's nonvolatile component content of the shining-material-containing aqueous base coat paint (B2) is lower than weight %, the sagging tends to occur. On the other hand, in the case where the paint's nonvolatile component content of the shining-material-containing aqueous
produced by CLARIANT (JAPAN) K. K.). It is the polyether urethane resins that are favorable particularly of these. In the case where the amount of the rheology control agent in the aqueous base coat paint (B2) is smaller than the aforementioned range, it follows that the Ti value is so low as to fail to sufficiently provide the metal-tone aesthetic appearance and the invisibility of aluminum flakes. On the other hand, in the case where the amount of the rheology control agent in the aqueous base coat paint (B2) is larger than the aforementioned range, it follows that problems are brought about in that the coating operation is difficult, and further in that the storage stability is deteriorated. More favorable modes are as follows:
when the rheology control agent is the polyether urethane resin, its content is in the range of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of the paint (B2); when the rheology control agent is the polyamide compound, its content is in the range of 2.0 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of the paint (B2); and when the rheology control agent is the polycarboxylic acid resin, its content is in the range of 2.0 to 6.0 phr in nonvolatile component weight relative to the resin's solid components of the paint (B2).
It is important that the aforementioned shining-material-containing aqueous base coat paint (B2) has a paint's nonvolatile component content (during the coating) of 10 to 20 weight % (favorably, 10 to 18 weight %) and a Ti value (thixotropic index) value) (during the coating) of not less than 3Ø Thereby, a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes can be formed. In the case where the paint's nonvolatile component content of the shining-material-containing aqueous base coat paint (B2) is lower than weight %, the sagging tends to occur. On the other hand, in the case where the paint's nonvolatile component content of the shining-material-containing aqueous
6 base coat paint (B2) is higher than 20 weight %, there appears a tendency toward a paint state ranging from a semi-gelled state to a gelled state, so that the coating operation is so difficult as to result in inferior smoothness of the resultant coating film or in failure to sufficiently provide the metal-tone aesthetic appearance. In the case where the Ti value of the shining-material-containing aqueous base coat paint (B2) is less than 3.0, the metal mottling or the sagging tends to occur to thus result in failure to sufficiently obtain the metal-tone aesthetic appearance and the invisibility of aluminum flakes. Incidentally, in the case where the Ti value of the shining-material-containing aqueous base coat paint (B2) is too large, there is a possibility that the coating operation may be difficult. Therefore, this Ti value is favorably not larger than 10Ø Incidentally, in the present invention, the aforementioned Ti value will do if it is measured by the method as below-mentioned in the description of Examples of some preferred embodiments.
It is favorable that the aforementioned shining-material-containing aqueous base coat paint (B2) contains a binder resin (B21) and a crosslinking agent (B22).
There is no especial limitation on the aforementioned binder resin (B21).
Resins which are conventionally used for aqueous base coat paints are usable as such.
However, hydroxyl-group-containing resins or hydroxyl-group-and-carboxyl-group-containing resins are favorable. Examples thereof include hydroxyl-group-containing or hydroxyl-group-and-carboxyl-group-containing acrylic resins or polyester resins.
Particularly, the hydroxyl-group-containing acrylic resins are favorable.
There is no especial limitation on the aforementioned crosslinking agent (B22).
Crosslinking agents which are conventionally used for aqueous base coat paints are usable as such. Examples thereof include melamine resins, polyisocyanate compounds, and polycarbodiimide compounds. Particularly of these, the melamine resins and the polycarbodiimide compounds are favorable for the aforementioned shining-material-containing aqueous base coat paint (B2).
It is favorable that the aforementioned shining-material-containing aqueous base coat paint (B2) contains a binder resin (B21) and a crosslinking agent (B22).
There is no especial limitation on the aforementioned binder resin (B21).
Resins which are conventionally used for aqueous base coat paints are usable as such.
However, hydroxyl-group-containing resins or hydroxyl-group-and-carboxyl-group-containing resins are favorable. Examples thereof include hydroxyl-group-containing or hydroxyl-group-and-carboxyl-group-containing acrylic resins or polyester resins.
Particularly, the hydroxyl-group-containing acrylic resins are favorable.
There is no especial limitation on the aforementioned crosslinking agent (B22).
Crosslinking agents which are conventionally used for aqueous base coat paints are usable as such. Examples thereof include melamine resins, polyisocyanate compounds, and polycarbodiimide compounds. Particularly of these, the melamine resins and the polycarbodiimide compounds are favorable for the aforementioned shining-material-containing aqueous base coat paint (B2).
7 Examples of the aforementioned melamine resins include alkoxymethylol melamines, specifically, such as methoxymethylol melamine, n-butoxymethylol melamine, isobutoxymethylol melamine, methoxybutoxymethylol melamine, and their condensation products. More favorable ones are the methoxymethylol melamine or n-butoxymethylol melamine having an average condensation degree of I to 4. However, melamine resins having at least one triazine ring would be free of especial limitation.
As to the aforementioned polycarbodiimide compounds, compounds having at least two carbodiimide groups (-N=C=N-) per molecule would do. Specific examples thereof include poly(4,4-diphenylmethanecarbodiimide), poly(3,3-dimethyl-4,4-biphenylmethanecarbodiimide), poly(tolylcarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(3,3-dimethyl-4,4-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(1,6-hexamethylenecarbodiimide), poly(4,4-methylenebiscyclohexylcarbodiimide), poly(1,4-tetramethylenecarbodiimide), poly(1,3-cyclohexylenecarbodiimide), poly(1,4-cyclohexylenecarbodiimide), poly(1,3-diisopropylphenylenecarbodiimide), poly(1-methyl-3,5-diisopropylphenylenecarbodiimide), poly(1,3,5-triethylphenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide).
A melamine resin (B221) or a mixture (B222) of the melamine resin and the polycarbodiimide compound of (melamine resin)/(polycarbodiimide compound) =
100/0 to 15/85 in nonvolatile component weight ratio is more favorable as the aforementioned crosslinking agent (B22). In the case where the ratio of the polycarbodiimide compound in the mixture (B222) of the melamine resin and the polycarbodiimide compound is more than the aforementioned range, there is a possibility that the gas resistance may be deteriorated. Therefore, the mixing ratio between the melamine resin and the polycarbodiimide compound is desirably set in
As to the aforementioned polycarbodiimide compounds, compounds having at least two carbodiimide groups (-N=C=N-) per molecule would do. Specific examples thereof include poly(4,4-diphenylmethanecarbodiimide), poly(3,3-dimethyl-4,4-biphenylmethanecarbodiimide), poly(tolylcarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(3,3-dimethyl-4,4-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(1,6-hexamethylenecarbodiimide), poly(4,4-methylenebiscyclohexylcarbodiimide), poly(1,4-tetramethylenecarbodiimide), poly(1,3-cyclohexylenecarbodiimide), poly(1,4-cyclohexylenecarbodiimide), poly(1,3-diisopropylphenylenecarbodiimide), poly(1-methyl-3,5-diisopropylphenylenecarbodiimide), poly(1,3,5-triethylphenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide).
A melamine resin (B221) or a mixture (B222) of the melamine resin and the polycarbodiimide compound of (melamine resin)/(polycarbodiimide compound) =
100/0 to 15/85 in nonvolatile component weight ratio is more favorable as the aforementioned crosslinking agent (B22). In the case where the ratio of the polycarbodiimide compound in the mixture (B222) of the melamine resin and the polycarbodiimide compound is more than the aforementioned range, there is a possibility that the gas resistance may be deteriorated. Therefore, the mixing ratio between the melamine resin and the polycarbodiimide compound is desirably set in
8 the aforementioned range.
The aforementioned aqueous base coat paint (B2) contains a shining material.
The aforementioned shining material is free of especial limitation, and hitherto publicly known shining materials are usable. For example, there can be used at least one member selected from the group consisting of aluminum flake pigments, metal-oxide-coated alumina flake pigments, metal-oxide-coated silica flake pigments, interfering mica pigments, colored mica pigments, metal titanium flake pigments, stainless flake pigments, metal-plated glass flake pigments, metal-oxide-coated glass flake pigments, hologram pigments, and flaky pigments which include cholesteric liquid crystal polymers. Incidentally, the content of the shining material in the aforementioned aqueous base coat paint (B2) is favorably in the range of 1 to weight % relative to the paint's solid components. In addition, similarly to the aforementioned solvent type base coat paint (B 1), if necessary, the aqueous base coat paint (B2) may contain such as the aforementioned color pigments and the aforementioned extenders within the range not spoiling the effects of the present invention.
Although not especially limited, the film thickness of the coating film (b2) formed from the aforementioned aqueous base coat paint (B2) is favorably set in the range of 1 to 6 m. In the case where the film thickness of the coating film (b2) is less than 1 m, there is a possibility that the hiding power may be so insufficient as to result in inferior design properties. On the other hand, in the case where the film thickness of the coating film (b2) is more than 6 m, there is a possibility that the orientational defect of the shining material in the aqueous base coat paint (B2) may tend to occur to thus result in failure to sufficiently obtain the metal-tone aesthetic appearance.
In the coating film formation process according to the present invention, it is important that, after the nonvolatile component content of the coating film (b2) formed from the shining-material-containing aqueous base coat paint (B2) has
The aforementioned aqueous base coat paint (B2) contains a shining material.
The aforementioned shining material is free of especial limitation, and hitherto publicly known shining materials are usable. For example, there can be used at least one member selected from the group consisting of aluminum flake pigments, metal-oxide-coated alumina flake pigments, metal-oxide-coated silica flake pigments, interfering mica pigments, colored mica pigments, metal titanium flake pigments, stainless flake pigments, metal-plated glass flake pigments, metal-oxide-coated glass flake pigments, hologram pigments, and flaky pigments which include cholesteric liquid crystal polymers. Incidentally, the content of the shining material in the aforementioned aqueous base coat paint (B2) is favorably in the range of 1 to weight % relative to the paint's solid components. In addition, similarly to the aforementioned solvent type base coat paint (B 1), if necessary, the aqueous base coat paint (B2) may contain such as the aforementioned color pigments and the aforementioned extenders within the range not spoiling the effects of the present invention.
Although not especially limited, the film thickness of the coating film (b2) formed from the aforementioned aqueous base coat paint (B2) is favorably set in the range of 1 to 6 m. In the case where the film thickness of the coating film (b2) is less than 1 m, there is a possibility that the hiding power may be so insufficient as to result in inferior design properties. On the other hand, in the case where the film thickness of the coating film (b2) is more than 6 m, there is a possibility that the orientational defect of the shining material in the aqueous base coat paint (B2) may tend to occur to thus result in failure to sufficiently obtain the metal-tone aesthetic appearance.
In the coating film formation process according to the present invention, it is important that, after the nonvolatile component content of the coating film (b2) formed from the shining-material-containing aqueous base coat paint (B2) has
9 reached not lower than 70 weight %, the top clear paint is coated onto the coating film (b2). In the case where the top clear paint is coated while the nonvolatile component content of the coating film (b2) is lower than 70 weight %, then it follows that the top clear paint is repelled by water remaining in the coating film (b2) and it is therefore difficult to form the clear coating film. Incidentally, such as adjustment of the setting time, or air blowing, or preheating (usually, at 80 C for about 5 to about 10 minutes), will do for the nonvolatile component content of the coating film (b2) to come in the aforementioned range.
The top clear paint for forming the third coating film layer in the coating film formation process according to the present invention is not especially limited. Top clear paints which are conventionally used are usable as such. However, favorable examples thereof include at least one member selected from among 1-package polyurethane paints, 2-package polyurethane paints, melamine resin curing paints, and acid-epoxy curing paints (e.g. a solvent type clear paint such as described in JP-B-019315/1996 (Kokoku), which includes a carboxyl-group-containing polymer and an epoxy-group-containing polymer; examples of commercially available ones include "MACFLOW (Registered Trademark)-0-330 CLEAR" produced by NIPPON PAINT CO., LTD.). Incidentally, the top clear paint may be any of solvent type paints, aqueous paints, and powder paints, so there is no limitation on its paint form.
Although not especially limited, the film thickness of the clear coating film formed from the aforementioned top clear paint is favorably set in the range of 10 to 60 m, more favorably 20 to 50 m. In the case where the film thickness of the clear coating film is less than 10 m, there is a possibility that there may occur problems of such as inferior coating film appearance and durability deterioration.
On the other hand, in the case where the film thickness of the clear coating film is more than 60 m, there is a possibility that the sagging may tend to occur to thus cause inconveniences of the coating operation.
Incidentally, each of the aforementioned solvent type base coat paint (Bl), the aforementioned shining-material-containing aqueous base coat paint (B2), and the aforementioned top clear paint may contain other components (e.g.:
crosslinking agents other than the aforementioned ones; surface conditioners; rheology control agents other than the aforementioned ones; ultraviolet absorbing agents; photo stabilizing agents; antioxidants; curing catalysts) which are conventionally added as additives for paints besides the aforementioned components, if necessary.
In the coating film formation process according to the present invention, the simultaneous baking of the three layers of coating films (coating film (bl), coating film (b2), and clear coating film) fonned in the above ways is carried out.
The heating temperature or heating duration in the baking is not especially limited.
However, for example, in the case where the 1-package polyurethane paint or 2-package polyurethane paint is used as the clear paint, it is enough that the heating is carried out at 60 to 120 C for 10 to 30 minutes. In the case where the melamine resin curing paint or acid-epoxy curing paint is used as the clear paint, it is enough that the heating is carried out at 120 to 160 C for 10 to 30 minutes.
The substrate to which the coating film formation process according to the present invention is applicable is not especially limited. Examples thereof include:
metal substrates such as iron, aluminum, copper, and stainless steel; and plastic substrates such as polyolefins, ABS, polycarbonates, and polyurethanes. In addition, on surfaces of these substrates for the coating films to be formed on, there may beforehand be formed such as a primer layer and an intermediate coating film layer, for example, by coating such as a primer, a cationic electrocoating paint, and an intermediate coat paint.
In the coating film formation process according to the present invention, the method for coating each paint is not especially limited. It is enough to carry out the coating appropriately selected from among hitherto publicly known coating methods (e.g. spray, roll coater, brush coating, electrostatic coating) with consideration given Il to such as the form of the paint being used and the surface shape of the substrate.
The coated article according to the present invention is a coated article having a coating film, wherein the coating film is formed by the aforementioned coating film formation process according to the present invention. Accordingly, the coated article according to the present invention is provided with the excellent metal-tone aesthetic appearance and the excellent invisibility of aluminum flakes and has the good design properties.
(Effects and Advantages of the Invention):
The present invention can provide: a coating film formation process which enables the formation of a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes; and a coated article having the excelient design properties as obtained by this process.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the present invention is more specifically illustrated by the following Examples of some preferred embodiments. However, the present invention is not limited to these in any way.
Incidentally, the nonvolatile component content and Ti value of the shining-material-containing aqueous base coat paint (B2) were determined in the following ways.
(Nonvolatile component content): In accordance with JIS-K-5601-1-2, there was measured a nonvolatile component content given when the paint was heated at 105 C for 3 hours.
(Ti value): The viscosities of the paint were measured at 20 C, numbers of revolutions = 6 rpm and 60 rpm with a Brookfield-viscometer ("RC-100" produced by TOKI SANGYO CO., LTD.) to calculate a value of (viscosity value measured at number of revolutions = 6 rpm)/(viscosity value measured at number of revolutions =
60 rpm).
(Examples 1 to 9 and Comparative Examples 1 to 5):
Coating films were formed by coating, in the 3-coat-and-l-bake manner, each paint (B 1) as shown in Tables 1 to 3, each paint (B2) as prepared in the following way, and each clear paint as shown in Tables 1 to 3. Specifically, each coating film (b 1) was formed by spraywise coating each solvent type base coat paint (B 1) onto each substrate, as shown in Tables 1 to 3, so as to have a dried film thickness of 10 m. Then, each coating film (b 1) was left intact at 20 C for 1 minute (when the nonvolatile component content of each coating film (bl) (NV of bl) was each value as shown in Tables 1 to 3 (NV of b1 when each paint (B2) was coated) as a result of the adjustment of the vaporization speed by setting the thinner composition of each paint (B1) at each composition as shown in Tables 1 to 3 (composition as beforehand set so that the nonvolatile component content of the coating film would be each value as shown in Tables 1 to 3 (NV of bl when each paint (B2) was coated) when the coating film was left intact at 20 C for 1 minute after the paint had been spraywise coated so that the dried film thickness would be 10 m)). Immediately thereafter, each coating film (b2) was formed by spraywise coating each shining-material-containing aqueous base coat paint (B2) onto each coating film (bl) so as to have a dried film thickness of 4 m and then preheated at 80 C for a duration in the range of 5 to 10 minutes so that the nonvolatile component content of each coating film (b2) (NV of b2) would be each value as shown in Tables 1 to (NV of b2 when each top clear paint was coated). Thereafter, each clear coating film was fonned by spraywise coating each top clear paint onto each coating film (b2) so as to have a dried film thickness of 35 m. Then, each substrate, on which the three layers of coating films had been formed, was heated at 80 C for 20 minutes in the case of having used the below-mentioned 2K as the top clear paint and at 140 C for 20 minutes in the case of having used the below-mentioned MF as the top clear paint, thus canying out the simultaneous baking of the three layers of coating films.
Incidentally, each preheating condition (heating duration) for the nonvolatile component content of each coating film (b2) (NV of b2) to reach each value as shown in Tables 1 to 3 was determined in the following way. That is to say, a plurality of test pieces are prepared by spraywise coating each paint (B2) (being used) onto aluminum foil (its weight is represented by "x") so as to have a dried film thickness of 4 m, and then the test pieces are preheated at 80 C for their respective heating durations (minutes) as varied in the range of 5 to 10 minutes.
Immediately thereafter, the aluminum foil is folded lest the volatile components should escape, and then the weights of the test pieces are measured (these measured weights are represented by "a"). Next, the folded aluminum foil is spread and then heated at 105 C for 3 hours in accordance with JIS-K-5601-1-2. Thereafter, the weights of the test pieces are measured (these measured weights are represented by "b").
Then, as to each test piece, the nonvolatile component content was calculated in accordance with the expression "[(b - x)/(a - x)] x 100". The relations of the plurality of heating durations with the resultant nonvolatile component contents were plotted to draw a calibration curve, from which there was determined each heating duration for the nonvolatile component content to reach each desired value as shown in Tables 1 to 3 (NV of b2 when each top clear paint was coated).
The details of the paints (B 1), clear paints, and substrates as shown in Tables I
to 3, and the methods for preparing the paints (B2) as shown in Tables 1 to 3, are as follows.
Solvent type base coat naints (B1):
IK (1-package polyurethane paints): prepared by diluting a solvent type 1-package polyurethane base paint of blocked isocyanate-acrylic resin ("R301 Base"
produced by NIPPON BEE CHEMICAL CO., LTD.) with thinners (the compositional ratios (weight ratios) of ethyl acetate ester (EA)/3-ethoxy-3-ethylpropionate (EEP) are as shown in Tables 1 to 3) so that the viscosity would be 12 seconds/25 C-#4 Ford cup.
2K (2-package polyurethane paints): prepared by diluting a solvent type 2-package polyurethane base paint of polyisocyanate-acrylic resin ("R212 Base"
produced by NIPPON BEE CHEMICAL CO., LTD.) with thinners (the compositional ratios (weight ratios) of ethyl acetate ester (EA)/3-ethoxy-3-ethylpropionate (EEP) are as shown in Tables 1 to 3) so that the viscosity would be 12 seconds/25 C=#4 Ford cup.
MF (melamine resin curing paints): prepared by diluting a solvent type base paint of melamine-acrylic resin ("SUPERLAC (Registered Trademark) M-95"
produced by NIPPON PAINT CO., LTD.) with thinners (the compositional ratios (weight ratios) of an aromatic hydrocarbon solvent ("SOLVESO (Registered Trademark)-100" produced by EXXON CORPORATION (S100))/ethyl acetate ester (EA) are as shown in Tables 1 to 3) so that the viscosity would be 10 seconds/25 C=NK-2 cup.
Shinina-material-containing acLueous base coat paints(B2):
Paints (B2) used in Examples 1 to 7 and Comparative Examples I to 5:
prepared by: placing an aqueous base paint of melamine-acrylic resin ("AQUAREX
(Registered Trademark) AR2100" produced by NIPPON PAINT CO., LTD.:
including at least a hydroxyl-group-and-carboxyl-group-containing binder resin, a crosslinking agent, and a shining material) (having beforehand been diluted to a solid component content of 30 weight % with deionized water) into a container having a stirrer; and then adding thereto rheology control agents (as shown in Tables 1 to 3) and deionized water under stirring to thereby obtain undiluted liquids of the paints;
and then diluting, with deionized water, these undiluted liquids of the paints to the paint's nonvolatile component contents of the paints (B2) as shown in Tables 1 to 3.
Paint (B2) used in Example 8: prepared by: placing an aqueous base paint of melamine-carbodiimideacrylic resin ("KX-0076" produced by NIPPON BEE
CHEMICAL CO., LTD.: including at least a hydroxyl-group-and-carboxyl-group-containing binder resin, a crosslinking agent, and a shining material) (having beforehand been diluted to a solid component content of 25 weight % with deionized water) into a container having a stirrer; and then adding thereto a rheology control agent (as shown in Table 3) and deionized water under stirring to thereby obtain a undiluted liquid of the paint; and then diluting, with deionized water, this undiluted liquid of the paint to the paint's nonvolatile component content of the paint (B2) as shown in Table 3.
Paint (B2) used in Example 9: prepared by: placing an aqueous base paint of melamine-acrylic resin (the aforementioned "AQUAREX (Registered Trademark) AR2100") (having beforehand been diluted to a solid component content of 30 weight % with deionized water) into a container having a stirrer; and then adding thereto a crosslinking agent under stirring; and then further adding a rheology control agent (as shown in Table 3) and deionized water under stirring to thereby obtain a undiluted liquid of the paint; and then diluting, with deionized water, this undiluted liquid of the paint to the paint's nonvolatile component content of the paint (B2) as shown in Table 3.
Shown in Tables 1 to 3 are: the mixing ratios of the components used for the preparation of the paints (B2); the types (MF/CDlm weight ratios) of the crosslinking agents contained in the paints (B2); the types of the shining materials contained in the paints (B2); the rheology control agent contents of the paints (B2) (nonvolatile component contents (phr) of the rheology control agents relative to the resin's solid components of the paints (B2)); the paint's nonvolatile component contents of the paints (B2); and the Ti values of the paints (B2).
Incidentally, in Tables 1 to 3, there are used the following abbreviations.
Aqueous base paint AR2100: an aqueous base paint of melamine-acrylic resin (the aforementioned "AQUAREX (Registered Trademark) AR2100") (having beforehand been diluted to a solid component content of 30 weight % with deionized water) Aqueous base paint KX-0076: an aqueous base paint of melamine-carbodiimideacrylic resin (the aforementioned "KX-0076") (having beforehand been diluted to a solid component content of 25 weight % with deionized water) Rheology control agent UH-752: a polyether urethane resin ("ADEKANOL
(Registered Trademark) UH-752" produced by ASAHI DENKA CO., LTD., solid component content = 30 weight %) Rheology control agent ASE-60: a polycarboxylic acid resin ("PRIMAL
(Registered Trademark) ASE-60" produced by ROHM and HAAS JAPAN K. K., solid component content = 28 weight %) Crosslinking agent (CDIm): a polycarbodiimide compound ("ISS-1000"
produced by NIPPON PAINT CO., LTD., solid component content = 70.7 weight %, carbodiimide equivalent = 905) Crosslinking agent (MF): a melamine resin Shining material 1: an aluminum paste ("MH-8801" produced by ASAHI
KASEI CORPORATION, particle diameter = 16 m) Shining material 2: an aluminum paste ("91-0562" produced by TOYO
ALUMINUM K. K., particle diameter = 18 gm) Top clear paints:
2K (2-package polyurethane paint): prepared by diluting 100 weight parts of a solvent type 2-package polyurethane paint of polyisocyanate-acrylic resin ("R290S
CLEAR" produced by NIPPON BEE CHEMICAL CO., LTD.) with 17 weight parts of a thinner (methyl ethyl ketone/petroleum hydrocarbon solvent ("LAWS
(Registered Trademark)" produced by SHELL JAPAN K. K.) = 50/50 weight ratio).
MF (melamine resin curing paint): prepared by diluting a solvent type clear paint of melamine-acrylic resin ("SUPERLAC (Registered Trademark) 0-100"
produced by NIPPON PAINT CO., LTD.) with an aromatic hydrocarbon solvent ("SOLVESO (Registered Trademark)-100" produced by EXXON CORPORATION) so that the viscosity would be 26 seconds/25 C-NK-2 cup.
Substrates:
M: prepared by: electrocoating a cationic electrocoating paint ("POWER TOP
(Registered Trademark) V-50" produced by NIPPON PAINT CO., LTD.) onto a zinc-phosphated dull steel sheet so that the dried film thickness would be 25 m; and then baking the resultant coating film at 160 C for 30 minutes; and then, further thereonto, air-spray-coating an intermediate coat paint ("ORGA (Registered Trademark) P-5 Sealer" produced by NIPPON PAINT CO., LTD.) so that the dried film thickness would be 40 m; and then baking the resultant coating film at for 30 minutes.
PI: prepared by: washing a polypropylene substrate with isopropanol; and then drying it; and then, thereonto, spray-coating a chlorinated polypropylene solvent type primer ("RB116 PRIMER" produced by NIPPON BEE CHEMICAL CO., LTD.) so that the dried film thickness would be 8 m; and then drying the resultant coating film at 80 C for 10 minutes.
P2: prepared by: washing an ABS substrate with isopropanol; and then drying it; and then, thereonto, spray-coating a urethane lacquer solvent type primer ("R185-1 PRIMER" produced by NIPPON BEE CHEMICAL CO., LTD.) so that the dried film thickness would be 8 gm; and then drying the resultant coating film at 80 C for 15 minutes.
The evaluations about the coating films- formed in the above Examples and Comparative Examples, and the evaluations of the diluted states of the paints (B2) before coating, were carried out in the following ways. The results are shown in Tables 1 to 3.
<Metal-tone aesthetic appearance (IV value)>:
The IV values of the formed coating films were measured with an IV meter ("ALCOPE (Registered Trademark) LMR-200" produced by KANSAI PAINT CO., LTD.). In the case where the resultant IV value was less than 400, this measured IV
value was taken as the IV value of the formed coating film.
On the other hand, as to the coating film having an IV value of not less than 400 as measured with the above IV meter, it is difficult to measure the IV
value directly with the above IV meter. Therefore, the IV value was determined from a calibration curve as drawn on the basis of values as measured with a digital angle-varying glossmeter. Specifically, a plurality of test pieces for drawing the calibration curve were prepared (these test pieces had the same hue as the color of the paint as used for the formed coating film, but had a plurality of different IV
values). These were measured by the IV values with the above IV meter, and further their gloss values at an incident angle of 45 degrees and a light-receiving angle of 35 degrees were determined with the digital angle-varying glossmeter ("UGV-5D" produced by SUGA TEST INSTRUMENTS CO., LTD.), from which a graph of the gloss values versus the IV values was produced to draw the calibration curve. Next, similarly to the aforementioned test pieces, the gloss value of the formed coating film was measured at the same incident angle and light-receiving angle with the digital angle-varying glossmeter, and then the IV value which was determined from the resultant gloss value in accordance with the calibration curve was taken as the IV value of the formed coating film.
<Invisibility of aluminum flakes>:
The state of the existence of aluminum flakes in the surface of the formed coating film was observed with the eye to make a judgment on the following standards.
0: The aluminum flakes in the coating film exist in a uniformly dispersed state and are therefore invisible, so the coating film is finished with a metal tone.
X: The aluminum flakes in the coating film exist in the form of particles and are therefore mush visible, so the coating film is not finished with a metal tone.
<Appearance>:
The appearance of the formed coating film was observed with the eye to make a judgment on the following standards.
0: No abnormality of the appearance, such as metal mottling, luster mottling, or cratering, is seen.
X: An abnormality of the appearance, such as metal mottling, luster mottling, or cratering, is seen.
<Diluted state of paint (B2) before coating>:
The diluted state of the paint (B2), when it got coated, was observed with the eye to make a judgment on the following standards.
0: No abnormality, such as gelation, is seen.
z~,: Being in a semi-gelled state.
X: Being in an entirely gelled state.
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Various details of the invention may be changed without departing from its spirit not its scope. Furthermore, the foregoing description of the preferred embodiments according to the present invention is provided for the purpose of illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.
The top clear paint for forming the third coating film layer in the coating film formation process according to the present invention is not especially limited. Top clear paints which are conventionally used are usable as such. However, favorable examples thereof include at least one member selected from among 1-package polyurethane paints, 2-package polyurethane paints, melamine resin curing paints, and acid-epoxy curing paints (e.g. a solvent type clear paint such as described in JP-B-019315/1996 (Kokoku), which includes a carboxyl-group-containing polymer and an epoxy-group-containing polymer; examples of commercially available ones include "MACFLOW (Registered Trademark)-0-330 CLEAR" produced by NIPPON PAINT CO., LTD.). Incidentally, the top clear paint may be any of solvent type paints, aqueous paints, and powder paints, so there is no limitation on its paint form.
Although not especially limited, the film thickness of the clear coating film formed from the aforementioned top clear paint is favorably set in the range of 10 to 60 m, more favorably 20 to 50 m. In the case where the film thickness of the clear coating film is less than 10 m, there is a possibility that there may occur problems of such as inferior coating film appearance and durability deterioration.
On the other hand, in the case where the film thickness of the clear coating film is more than 60 m, there is a possibility that the sagging may tend to occur to thus cause inconveniences of the coating operation.
Incidentally, each of the aforementioned solvent type base coat paint (Bl), the aforementioned shining-material-containing aqueous base coat paint (B2), and the aforementioned top clear paint may contain other components (e.g.:
crosslinking agents other than the aforementioned ones; surface conditioners; rheology control agents other than the aforementioned ones; ultraviolet absorbing agents; photo stabilizing agents; antioxidants; curing catalysts) which are conventionally added as additives for paints besides the aforementioned components, if necessary.
In the coating film formation process according to the present invention, the simultaneous baking of the three layers of coating films (coating film (bl), coating film (b2), and clear coating film) fonned in the above ways is carried out.
The heating temperature or heating duration in the baking is not especially limited.
However, for example, in the case where the 1-package polyurethane paint or 2-package polyurethane paint is used as the clear paint, it is enough that the heating is carried out at 60 to 120 C for 10 to 30 minutes. In the case where the melamine resin curing paint or acid-epoxy curing paint is used as the clear paint, it is enough that the heating is carried out at 120 to 160 C for 10 to 30 minutes.
The substrate to which the coating film formation process according to the present invention is applicable is not especially limited. Examples thereof include:
metal substrates such as iron, aluminum, copper, and stainless steel; and plastic substrates such as polyolefins, ABS, polycarbonates, and polyurethanes. In addition, on surfaces of these substrates for the coating films to be formed on, there may beforehand be formed such as a primer layer and an intermediate coating film layer, for example, by coating such as a primer, a cationic electrocoating paint, and an intermediate coat paint.
In the coating film formation process according to the present invention, the method for coating each paint is not especially limited. It is enough to carry out the coating appropriately selected from among hitherto publicly known coating methods (e.g. spray, roll coater, brush coating, electrostatic coating) with consideration given Il to such as the form of the paint being used and the surface shape of the substrate.
The coated article according to the present invention is a coated article having a coating film, wherein the coating film is formed by the aforementioned coating film formation process according to the present invention. Accordingly, the coated article according to the present invention is provided with the excellent metal-tone aesthetic appearance and the excellent invisibility of aluminum flakes and has the good design properties.
(Effects and Advantages of the Invention):
The present invention can provide: a coating film formation process which enables the formation of a coating film excellent in the metal-tone aesthetic appearance and the invisibility of aluminum flakes; and a coated article having the excelient design properties as obtained by this process.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the present invention is more specifically illustrated by the following Examples of some preferred embodiments. However, the present invention is not limited to these in any way.
Incidentally, the nonvolatile component content and Ti value of the shining-material-containing aqueous base coat paint (B2) were determined in the following ways.
(Nonvolatile component content): In accordance with JIS-K-5601-1-2, there was measured a nonvolatile component content given when the paint was heated at 105 C for 3 hours.
(Ti value): The viscosities of the paint were measured at 20 C, numbers of revolutions = 6 rpm and 60 rpm with a Brookfield-viscometer ("RC-100" produced by TOKI SANGYO CO., LTD.) to calculate a value of (viscosity value measured at number of revolutions = 6 rpm)/(viscosity value measured at number of revolutions =
60 rpm).
(Examples 1 to 9 and Comparative Examples 1 to 5):
Coating films were formed by coating, in the 3-coat-and-l-bake manner, each paint (B 1) as shown in Tables 1 to 3, each paint (B2) as prepared in the following way, and each clear paint as shown in Tables 1 to 3. Specifically, each coating film (b 1) was formed by spraywise coating each solvent type base coat paint (B 1) onto each substrate, as shown in Tables 1 to 3, so as to have a dried film thickness of 10 m. Then, each coating film (b 1) was left intact at 20 C for 1 minute (when the nonvolatile component content of each coating film (bl) (NV of bl) was each value as shown in Tables 1 to 3 (NV of b1 when each paint (B2) was coated) as a result of the adjustment of the vaporization speed by setting the thinner composition of each paint (B1) at each composition as shown in Tables 1 to 3 (composition as beforehand set so that the nonvolatile component content of the coating film would be each value as shown in Tables 1 to 3 (NV of bl when each paint (B2) was coated) when the coating film was left intact at 20 C for 1 minute after the paint had been spraywise coated so that the dried film thickness would be 10 m)). Immediately thereafter, each coating film (b2) was formed by spraywise coating each shining-material-containing aqueous base coat paint (B2) onto each coating film (bl) so as to have a dried film thickness of 4 m and then preheated at 80 C for a duration in the range of 5 to 10 minutes so that the nonvolatile component content of each coating film (b2) (NV of b2) would be each value as shown in Tables 1 to (NV of b2 when each top clear paint was coated). Thereafter, each clear coating film was fonned by spraywise coating each top clear paint onto each coating film (b2) so as to have a dried film thickness of 35 m. Then, each substrate, on which the three layers of coating films had been formed, was heated at 80 C for 20 minutes in the case of having used the below-mentioned 2K as the top clear paint and at 140 C for 20 minutes in the case of having used the below-mentioned MF as the top clear paint, thus canying out the simultaneous baking of the three layers of coating films.
Incidentally, each preheating condition (heating duration) for the nonvolatile component content of each coating film (b2) (NV of b2) to reach each value as shown in Tables 1 to 3 was determined in the following way. That is to say, a plurality of test pieces are prepared by spraywise coating each paint (B2) (being used) onto aluminum foil (its weight is represented by "x") so as to have a dried film thickness of 4 m, and then the test pieces are preheated at 80 C for their respective heating durations (minutes) as varied in the range of 5 to 10 minutes.
Immediately thereafter, the aluminum foil is folded lest the volatile components should escape, and then the weights of the test pieces are measured (these measured weights are represented by "a"). Next, the folded aluminum foil is spread and then heated at 105 C for 3 hours in accordance with JIS-K-5601-1-2. Thereafter, the weights of the test pieces are measured (these measured weights are represented by "b").
Then, as to each test piece, the nonvolatile component content was calculated in accordance with the expression "[(b - x)/(a - x)] x 100". The relations of the plurality of heating durations with the resultant nonvolatile component contents were plotted to draw a calibration curve, from which there was determined each heating duration for the nonvolatile component content to reach each desired value as shown in Tables 1 to 3 (NV of b2 when each top clear paint was coated).
The details of the paints (B 1), clear paints, and substrates as shown in Tables I
to 3, and the methods for preparing the paints (B2) as shown in Tables 1 to 3, are as follows.
Solvent type base coat naints (B1):
IK (1-package polyurethane paints): prepared by diluting a solvent type 1-package polyurethane base paint of blocked isocyanate-acrylic resin ("R301 Base"
produced by NIPPON BEE CHEMICAL CO., LTD.) with thinners (the compositional ratios (weight ratios) of ethyl acetate ester (EA)/3-ethoxy-3-ethylpropionate (EEP) are as shown in Tables 1 to 3) so that the viscosity would be 12 seconds/25 C-#4 Ford cup.
2K (2-package polyurethane paints): prepared by diluting a solvent type 2-package polyurethane base paint of polyisocyanate-acrylic resin ("R212 Base"
produced by NIPPON BEE CHEMICAL CO., LTD.) with thinners (the compositional ratios (weight ratios) of ethyl acetate ester (EA)/3-ethoxy-3-ethylpropionate (EEP) are as shown in Tables 1 to 3) so that the viscosity would be 12 seconds/25 C=#4 Ford cup.
MF (melamine resin curing paints): prepared by diluting a solvent type base paint of melamine-acrylic resin ("SUPERLAC (Registered Trademark) M-95"
produced by NIPPON PAINT CO., LTD.) with thinners (the compositional ratios (weight ratios) of an aromatic hydrocarbon solvent ("SOLVESO (Registered Trademark)-100" produced by EXXON CORPORATION (S100))/ethyl acetate ester (EA) are as shown in Tables 1 to 3) so that the viscosity would be 10 seconds/25 C=NK-2 cup.
Shinina-material-containing acLueous base coat paints(B2):
Paints (B2) used in Examples 1 to 7 and Comparative Examples I to 5:
prepared by: placing an aqueous base paint of melamine-acrylic resin ("AQUAREX
(Registered Trademark) AR2100" produced by NIPPON PAINT CO., LTD.:
including at least a hydroxyl-group-and-carboxyl-group-containing binder resin, a crosslinking agent, and a shining material) (having beforehand been diluted to a solid component content of 30 weight % with deionized water) into a container having a stirrer; and then adding thereto rheology control agents (as shown in Tables 1 to 3) and deionized water under stirring to thereby obtain undiluted liquids of the paints;
and then diluting, with deionized water, these undiluted liquids of the paints to the paint's nonvolatile component contents of the paints (B2) as shown in Tables 1 to 3.
Paint (B2) used in Example 8: prepared by: placing an aqueous base paint of melamine-carbodiimideacrylic resin ("KX-0076" produced by NIPPON BEE
CHEMICAL CO., LTD.: including at least a hydroxyl-group-and-carboxyl-group-containing binder resin, a crosslinking agent, and a shining material) (having beforehand been diluted to a solid component content of 25 weight % with deionized water) into a container having a stirrer; and then adding thereto a rheology control agent (as shown in Table 3) and deionized water under stirring to thereby obtain a undiluted liquid of the paint; and then diluting, with deionized water, this undiluted liquid of the paint to the paint's nonvolatile component content of the paint (B2) as shown in Table 3.
Paint (B2) used in Example 9: prepared by: placing an aqueous base paint of melamine-acrylic resin (the aforementioned "AQUAREX (Registered Trademark) AR2100") (having beforehand been diluted to a solid component content of 30 weight % with deionized water) into a container having a stirrer; and then adding thereto a crosslinking agent under stirring; and then further adding a rheology control agent (as shown in Table 3) and deionized water under stirring to thereby obtain a undiluted liquid of the paint; and then diluting, with deionized water, this undiluted liquid of the paint to the paint's nonvolatile component content of the paint (B2) as shown in Table 3.
Shown in Tables 1 to 3 are: the mixing ratios of the components used for the preparation of the paints (B2); the types (MF/CDlm weight ratios) of the crosslinking agents contained in the paints (B2); the types of the shining materials contained in the paints (B2); the rheology control agent contents of the paints (B2) (nonvolatile component contents (phr) of the rheology control agents relative to the resin's solid components of the paints (B2)); the paint's nonvolatile component contents of the paints (B2); and the Ti values of the paints (B2).
Incidentally, in Tables 1 to 3, there are used the following abbreviations.
Aqueous base paint AR2100: an aqueous base paint of melamine-acrylic resin (the aforementioned "AQUAREX (Registered Trademark) AR2100") (having beforehand been diluted to a solid component content of 30 weight % with deionized water) Aqueous base paint KX-0076: an aqueous base paint of melamine-carbodiimideacrylic resin (the aforementioned "KX-0076") (having beforehand been diluted to a solid component content of 25 weight % with deionized water) Rheology control agent UH-752: a polyether urethane resin ("ADEKANOL
(Registered Trademark) UH-752" produced by ASAHI DENKA CO., LTD., solid component content = 30 weight %) Rheology control agent ASE-60: a polycarboxylic acid resin ("PRIMAL
(Registered Trademark) ASE-60" produced by ROHM and HAAS JAPAN K. K., solid component content = 28 weight %) Crosslinking agent (CDIm): a polycarbodiimide compound ("ISS-1000"
produced by NIPPON PAINT CO., LTD., solid component content = 70.7 weight %, carbodiimide equivalent = 905) Crosslinking agent (MF): a melamine resin Shining material 1: an aluminum paste ("MH-8801" produced by ASAHI
KASEI CORPORATION, particle diameter = 16 m) Shining material 2: an aluminum paste ("91-0562" produced by TOYO
ALUMINUM K. K., particle diameter = 18 gm) Top clear paints:
2K (2-package polyurethane paint): prepared by diluting 100 weight parts of a solvent type 2-package polyurethane paint of polyisocyanate-acrylic resin ("R290S
CLEAR" produced by NIPPON BEE CHEMICAL CO., LTD.) with 17 weight parts of a thinner (methyl ethyl ketone/petroleum hydrocarbon solvent ("LAWS
(Registered Trademark)" produced by SHELL JAPAN K. K.) = 50/50 weight ratio).
MF (melamine resin curing paint): prepared by diluting a solvent type clear paint of melamine-acrylic resin ("SUPERLAC (Registered Trademark) 0-100"
produced by NIPPON PAINT CO., LTD.) with an aromatic hydrocarbon solvent ("SOLVESO (Registered Trademark)-100" produced by EXXON CORPORATION) so that the viscosity would be 26 seconds/25 C-NK-2 cup.
Substrates:
M: prepared by: electrocoating a cationic electrocoating paint ("POWER TOP
(Registered Trademark) V-50" produced by NIPPON PAINT CO., LTD.) onto a zinc-phosphated dull steel sheet so that the dried film thickness would be 25 m; and then baking the resultant coating film at 160 C for 30 minutes; and then, further thereonto, air-spray-coating an intermediate coat paint ("ORGA (Registered Trademark) P-5 Sealer" produced by NIPPON PAINT CO., LTD.) so that the dried film thickness would be 40 m; and then baking the resultant coating film at for 30 minutes.
PI: prepared by: washing a polypropylene substrate with isopropanol; and then drying it; and then, thereonto, spray-coating a chlorinated polypropylene solvent type primer ("RB116 PRIMER" produced by NIPPON BEE CHEMICAL CO., LTD.) so that the dried film thickness would be 8 m; and then drying the resultant coating film at 80 C for 10 minutes.
P2: prepared by: washing an ABS substrate with isopropanol; and then drying it; and then, thereonto, spray-coating a urethane lacquer solvent type primer ("R185-1 PRIMER" produced by NIPPON BEE CHEMICAL CO., LTD.) so that the dried film thickness would be 8 gm; and then drying the resultant coating film at 80 C for 15 minutes.
The evaluations about the coating films- formed in the above Examples and Comparative Examples, and the evaluations of the diluted states of the paints (B2) before coating, were carried out in the following ways. The results are shown in Tables 1 to 3.
<Metal-tone aesthetic appearance (IV value)>:
The IV values of the formed coating films were measured with an IV meter ("ALCOPE (Registered Trademark) LMR-200" produced by KANSAI PAINT CO., LTD.). In the case where the resultant IV value was less than 400, this measured IV
value was taken as the IV value of the formed coating film.
On the other hand, as to the coating film having an IV value of not less than 400 as measured with the above IV meter, it is difficult to measure the IV
value directly with the above IV meter. Therefore, the IV value was determined from a calibration curve as drawn on the basis of values as measured with a digital angle-varying glossmeter. Specifically, a plurality of test pieces for drawing the calibration curve were prepared (these test pieces had the same hue as the color of the paint as used for the formed coating film, but had a plurality of different IV
values). These were measured by the IV values with the above IV meter, and further their gloss values at an incident angle of 45 degrees and a light-receiving angle of 35 degrees were determined with the digital angle-varying glossmeter ("UGV-5D" produced by SUGA TEST INSTRUMENTS CO., LTD.), from which a graph of the gloss values versus the IV values was produced to draw the calibration curve. Next, similarly to the aforementioned test pieces, the gloss value of the formed coating film was measured at the same incident angle and light-receiving angle with the digital angle-varying glossmeter, and then the IV value which was determined from the resultant gloss value in accordance with the calibration curve was taken as the IV value of the formed coating film.
<Invisibility of aluminum flakes>:
The state of the existence of aluminum flakes in the surface of the formed coating film was observed with the eye to make a judgment on the following standards.
0: The aluminum flakes in the coating film exist in a uniformly dispersed state and are therefore invisible, so the coating film is finished with a metal tone.
X: The aluminum flakes in the coating film exist in the form of particles and are therefore mush visible, so the coating film is not finished with a metal tone.
<Appearance>:
The appearance of the formed coating film was observed with the eye to make a judgment on the following standards.
0: No abnormality of the appearance, such as metal mottling, luster mottling, or cratering, is seen.
X: An abnormality of the appearance, such as metal mottling, luster mottling, or cratering, is seen.
<Diluted state of paint (B2) before coating>:
The diluted state of the paint (B2), when it got coated, was observed with the eye to make a judgment on the following standards.
0: No abnormality, such as gelation, is seen.
z~,: Being in a semi-gelled state.
X: Being in an entirely gelled state.
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Various details of the invention may be changed without departing from its spirit not its scope. Furthermore, the foregoing description of the preferred embodiments according to the present invention is provided for the purpose of illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.
Claims (4)
1. A coating film formation process, which is a coating film formation process comprising the steps of coating a solvent type base coat paint (B1) onto a substrate to thus form a coating film (b1) thereon; and then, after the nonvolatile component content of the coating film (b1) has reached not lower than 40 weight %, coating a shining-material-containing aqueous base coat paint (B2) onto the coating film (b1) to thus form a coating film (b2) thereon; and then, after the nonvolatile component content of the coating film (b2) has reached not lower than 70 weight %, coating a top clear paint onto the coating film (b2) to thus form a clear coating film thereon; and thereafter carrying out simultaneous baking of the formed three layers of coating films;
with the process being characterized in that, as the shining-material-containing aqueous base coat paint (B2), there is used a paint which contains a rheology control agent of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components and has a paint's nonvolatile component content of 10 to 20 weight %
and a thixotropic index value of not less than 3Ø
with the process being characterized in that, as the shining-material-containing aqueous base coat paint (B2), there is used a paint which contains a rheology control agent of 0.5 to 6.0 phr in nonvolatile component weight relative to the resin's solid components and has a paint's nonvolatile component content of 10 to 20 weight %
and a thixotropic index value of not less than 3Ø
2. A coating film formation process according to claim 1, wherein the shining-material-containing aqueous base coat paint (B2) contains a binder resin (B21) and a crosslinking agent (B22), wherein the binder resin (B21) includes a hydroxyl-group-containing resin or hydroxyl-group-and-carboxyl-group-containing resin, and wherein the crosslinking agent (B22) includes a melamine resin (B221) or a mixture (B222) of the melamine resin and a polycarbodiimide compound of (melamine resin)/(polycarbodiimide compound) = 100/0 to 15/85 in nonvolatile component weight ratio.
3. A coating film formation process according to claim 1 or 2, wherein the solvent type base coat paint (B1) is at least one member selected from among 1-package polyurethane paints, 2-package polyurethane paints, and melamine resin curing paints.
4. A coated article, which is a coated article having a coating film, wherein the coating film is formed by the coating film formation process as recited in any one of claims 1 to 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003-153993 | 2003-05-30 | ||
| JP2003153993A JP4063715B2 (en) | 2003-05-30 | 2003-05-30 | Coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2468639A1 CA2468639A1 (en) | 2004-11-30 |
| CA2468639C true CA2468639C (en) | 2008-09-09 |
Family
ID=33128296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002468639A Expired - Fee Related CA2468639C (en) | 2003-05-30 | 2004-05-27 | Coating film formation process and coated article |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20040241450A1 (en) |
| EP (1) | EP1482014B1 (en) |
| JP (1) | JP4063715B2 (en) |
| CN (1) | CN100342984C (en) |
| CA (1) | CA2468639C (en) |
| DE (1) | DE602004030858D1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10326353A1 (en) * | 2003-06-12 | 2005-01-05 | Basf Coatings Ag | Solvent-containing, thermally and / or curable with actinic radiation, opaque pigments covering coating materials, processes for their preparation and their use |
| GB2420995B (en) * | 2004-12-08 | 2007-03-21 | Aerocoat Ltd | Method of coating a surface |
| JP2006263520A (en) * | 2005-03-22 | 2006-10-05 | Mazda Motor Corp | Method for forming glitter coating film |
| KR101222947B1 (en) | 2005-06-30 | 2013-01-17 | 엘지디스플레이 주식회사 | Solvent for printing, pattern composition for printing, and pattering method using the same |
| DE102007023539A1 (en) * | 2007-05-18 | 2008-11-20 | Basf Coatings Ag | Aqueous, pigmented coating compositions, process for their preparation and their use for the production of multicoat paint systems |
| EP2225313B1 (en) * | 2007-12-20 | 2016-04-13 | Coatings Foreign IP Co. LLC | Process for producing a multilayer coating |
| CN101977973A (en) | 2007-12-20 | 2011-02-16 | 纳幕尔杜邦公司 | Process for producing a multilayer coating |
| GB2457241A (en) * | 2008-02-05 | 2009-08-12 | Sun Chemical Ltd | Printing ink or varnish for printing value documents |
| JP5324642B2 (en) * | 2008-03-25 | 2013-10-23 | スリーエム イノベイティブ プロパティズ カンパニー | Paint film composite and method for producing the same |
| DE102008054283A1 (en) * | 2008-11-03 | 2010-06-02 | Basf Coatings Japan Ltd., Yokohama | Color and / or effect multi-layer coatings with pigment-free coatings as filler replacement, their preparation and use |
| JP2014033980A (en) * | 2012-08-07 | 2014-02-24 | Nippon Paint Co Ltd | Multilayer coating film formation method and multilayer coating film obtained from the same |
| JP6082333B2 (en) * | 2012-10-16 | 2017-02-15 | 株式会社神戸製鋼所 | Water-based resin coating laminated metal sheet |
| US9815084B2 (en) * | 2013-05-13 | 2017-11-14 | Nissan Motor Co., Ltd. | Clear coating method, coating method, and coating film structure |
| CN108367312B (en) * | 2015-12-25 | 2021-06-08 | 关西涂料株式会社 | Method for forming multilayer coating film |
| DE102016224402A1 (en) * | 2016-12-07 | 2018-06-07 | Aktiebolaget Skf | Bearing component and method for increasing the resistance of a bearing component |
| WO2020153057A1 (en) * | 2019-01-21 | 2020-07-30 | 関西ペイント株式会社 | Method for forming multi-layer coating film |
| CN111978779A (en) * | 2019-05-05 | 2020-11-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Pearlescent powder, pearlescent paint and TPO product coated with pearlescent paint |
| JP7519160B2 (en) | 2019-09-03 | 2024-07-19 | 関西ペイント株式会社 | Multi-layer coating method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104922A (en) * | 1990-10-22 | 1992-04-14 | E. I. Du Pont De Nemours And Company | Stable aqueous aluminum flake dispersion |
| CN1161707A (en) * | 1994-10-22 | 1997-10-08 | 巴斯福拉克和法本股份公司 | Filler component for use in aqueous base paints |
| DE4437841A1 (en) * | 1994-10-22 | 1996-04-25 | Basf Lacke & Farben | Filler component for use in aqueous basecoats |
| DE19741554B4 (en) * | 1997-09-20 | 2005-04-14 | Basf Coatings Ag | A curable coating composition and method of making a protective coating |
| US6296706B1 (en) * | 1999-11-15 | 2001-10-02 | Ppg Industries Ohio, Inc. | Method and apparatus for dynamically coating a substrate |
-
2003
- 2003-05-30 JP JP2003153993A patent/JP4063715B2/en not_active Expired - Fee Related
-
2004
- 2004-05-20 US US10/850,189 patent/US20040241450A1/en not_active Abandoned
- 2004-05-27 DE DE200460030858 patent/DE602004030858D1/en not_active Expired - Lifetime
- 2004-05-27 EP EP20040012600 patent/EP1482014B1/en not_active Revoked
- 2004-05-27 CA CA002468639A patent/CA2468639C/en not_active Expired - Fee Related
- 2004-05-28 CN CNB2004100714417A patent/CN100342984C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP4063715B2 (en) | 2008-03-19 |
| EP1482014B1 (en) | 2011-01-05 |
| CA2468639A1 (en) | 2004-11-30 |
| JP2004351359A (en) | 2004-12-16 |
| CN1575867A (en) | 2005-02-09 |
| DE602004030858D1 (en) | 2011-02-17 |
| US20040241450A1 (en) | 2004-12-02 |
| CN100342984C (en) | 2007-10-17 |
| EP1482014A1 (en) | 2004-12-01 |
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